Bubble nucleation in polymer–CO2 mixtures

We combine density-functional theory with the string method to calculate the minimum free energy path of bubble nucleation in two polymer–CO2 mixture systems, poly(methyl methacrylate) (PMMA)–CO2 and polystyrene (PS)–CO2. Nucleation is initiated by saturating the polymer liquid with high pressure CO2 and subsequently reducing the pressure to ambient condition. Below a critical temperature (Tc), we find that there is a discontinuous drop in the nucleation barrier as a function of increased initial CO2 pressure (P0), as a result of an underlying metastable transition from a CO2-rich-vapor phase to a CO2-rich-liquid phase. The nucleation barrier is generally higher for PS–CO2 than for PMMA–CO2 under the same temperature and pressure conditions, and both higher temperature and higher initial pressure are required to lower the nucleation barrier for PS–CO2 to experimentally relevant ranges. Classical nucleation theory completely fails to capture the structural features of the bubble nucleus and severely underestimates the nucleation barrier.